Wax composition containing a completely esterified styrene-maleic anhydride heteropolymer



Patented Apr. 2 7, 1954 2,676,934 ice COMPOSITION CONTAINING A. COM- PIJETELY ESTERIFIED 'STYRENE-MAIZEIC' ANHYDRIDE HETEROPOLYMER John Mann ButleryDayton,v Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application November 23, 1951, Serial No. 257,952

1 Claim; (Cl. zoo-2&5)

This. invention relates to wax or wax-containing compositions having .improvedtoughness and relates particularly to compositions which are adapted to be used in connection with the impregnation and coating of'fibrous products, such as paper; textiles, leather and wood;

' An object of this-invention is to improve the physicai properties ofhydrocarbon wax compositi'ons containing said-=waxes of various types and proportions. Anothery'object is to provide compositions which are adapted to impregnating paper orpaperprcducts, particularly for impregnatingpaper which i's-ito be used for wrapping or forthe forming of objects of paper where some degree ofadhesivenessis required.

It has'now" been discovered that certain esterifie'd styrene-maleic anhydride resins are, in certain proportions, completely compatible with hydrocarbon waxes, particularly paraflin'ic waxes, and that the homogeneous blends thereof have unusual and very desirable physical properties, such as improved tensile strength, deflection. clarity and gloss, .andadhesion. to. paper, metal, wood and synthetic resins. Suitable waxes are the paraffin waxes, including .both the microcrystallinewaxes andrthe lower melting paraffin waxes and the earth waxes such as ceresin or ozoke'rite. The new compositions maybe made by mixing from 0.10 to=-30.0, per cent by weight of the esterified styrene-maleic anhydride resin with from 99.90% to'70.0% of the wax, but preferred compositions will have 80 or more per cent of the wax, the percentages being, based on the total wax and esterified styrene-'maleic anhydride resin in the composition. Various other modifying agents such as fillers, plasticizers,

pigments and adhesivesmay be added as desired in the manner conventional in the art of coating compositions.

The esterified styrene-maleic anhydride resins used in the practice of this invention are those in which a heteropoly'mer of styrene and maleic anhydride has been esterified with a saturated,

unsubstituted aliphaticalcohol of from; B to '16 carbon atoms. Styrene-maleic anhydrideh'eteropolymers are well known-in the art. 'I'heyare obtainable by subjecting--to polymerizing conditions a mixture of styrene and maleic anhydride, substantially as described in the Fikentscher U. S. Patent No. 1,976,679 and the Voss U. S. Patent No. 2,047,398. For the present purposes, the heteropolymerof one'mole of styrene with one mole of maleic anhydride is preferred. Such a heteropolymeris. composed of 'a number of polymerized groups having the probable formula H- -Qn-cc-:0H

. 2- Esterification of the maleic anhydride-styreno copolymer with aliphatic, unsubstituted, saturated: alcohols of from 8' to 1'6. carbon atomsyiel'ds products which contain a plurality of units containing the probable formula inwhich Y isan alkyl radical. of from 8 to 16 carbon atoms.

Alcohols which-may be employed for theesterification include the straight chain, normal tatty alcohols such as decyl, hendecyl, dodecyl, trideoyl, tetradecyl or hexadecylalcohol or branched chain alcohols such. as 2-butyloctanol-l,2,6,8- trimethylnonanol-i, or tert-dodecyl alcohol. Mixtures of the alcohols may be used. Reaction of the alcohol with the styrene maleic anhydride heteropolymer to yield the useful esterified heteropolymers is-effected by heatinga mixture of the two in the presence of an esteri-fying catalyst, e. g., phosphoric acid, sulfuric acid or 4-toluenesulfonic acid and, advantageously; in the presence of a small amount, e. g., up to 5 per cent, of a material such as xylene or toluene to aid. in removing reaction water. In order to completely esterify the styrene-maleic anhydride heteropolymer, it is generally necessary to employ in the reaction mixture at least a slight excess of the theoretically required amount of alcohol, 1. e., two moles of alcohol for each of the maleic anhydricle groups of the heteropolymer.

The present compositions may be applied to paper, textiles, or generally any fibrous material by impregnation or coating such as by dipping .the material into the molten composition, or in solutions of the composition in suitable solvents.

. ,plication may be made by machine in which continuous webs or sheets of the material to be treated are drawn through the baths of the compounds herein disclosed, or by callender rolls, heated if desiredywhich force the solid composition into the interstices of the fibrous composition being impregnated. Application to the surface of papers, felt, cloth,-or other fabrics may be accomplished by use of aspreading technique,

" whereby the thickness of the application is regulated by means of adjustable spreader bars or doctor blades in the manner well known to the art.

Suitable hydrocarbon waxes for blending in accordance with this invention are the waxes I having melting or softening points over 3 and preferably those which remain relatively hard and rigid at temperatures up to 120 F. Of particular importance are the microcrystalline parafiin waxes having melting points between 140 F. and 200 F., the low melting paraifins, and the hydrocarbon earth waxes, for example, refined ceresin.

Further details of the practice of this invention are set forth with respect to the following specific was melted with to parts by weight of the LSMA of Example 1. Thereafter 15 parts by weight of hydrogenated glyceryl abietate and parts of butyl phthalyl butyl glycolate were added and thoroughly blended. This product was used to impregnate paper which was valuable in wrapping cheese because of its ability to resist cracking and crushing, and to withstand the rough handling encountered in shipping operations.

cloud point property. In small concentrations the LSMA has a pronounced efiect on increasing the tensile strength of the wax. The LSMA modified wax shows up very well on the slow deflection bend test.

Example 2 Fifty parts by weight of a microcrystalline paraffin wax having a melting point of 172 F examples. I Example 3 Example 1 A coated paper useful in wrapping bread and Styrene-maleic anhydride resin prepared from other food StuiTS y reason of it mor d es v substantially equimolar" proportions of styrene noturo Was prepared y blendlng t e ol owing and maleic anhydride and having a solution visl5 materials cosity of 80 cps. was esterified with Lorol, a Parts by Welght mixture of C8 to C16 alcohols prepared by hydro- Mlcioclystollme Wax, F 20 genation of coconut oil, employing the following L (Example 1) 8 procedure: Parafiin wax, M. P. 146-148" F I to a 00 flask equipped With agitator, 20 While the present invention has been disclosed t e Deon-Stark Water trap and 0011' with particular reference to the incorporation of 61611581 were placed molo) of the W the Lorol ester of styrene and maleic anhydride rene-maleic anhydride resin, 41 g. (0.22 mole) of t hydrocarbon waxes, th 1 oh 1 employed for the Lo ol, 69 g- O Xylene and 1% (0-33 ml) the preparation of this ester being particularly of sulfuric acid and the resulting mixture was readily vailable equally good re lts are obheated at a temperature of 146 C. for about 15 t m b incgrporation ith the hydrocarbon hours- The product then mixed with waxes of from 0.10 per cent to per cent of other butyl alcohol and the resulting precipitated prodesters of styrene m3,1ej c anhydride h t o 1 uct dried i a V u oVeIl- The dliod material mers and alcohols of from 8 to 16 carbon atoms. was the substantially pure Lorol ester of styrene- 30 Thus instead of t Lorol te of Example 1, maleic anhydride heteropolymer. It will hereinth may be prepared in like manner C12 fatty afte be designated s LSMA- alcohol esters of styrene-maleic anhydride hetero- I co p of s ester il'lto Daraflin Wax .polymer such as the n-dodecyl ester or the tetra- Wos effected y t g 2 g. of the ester with decyl ester, or esters of styrene-maleic anhydride of p f W x o about The eSteTiheteropolymers with alcohols of higher or lower fled hetelopolymol dissolved in the wax and carbon content such as decyl alcohol, hexadecyl mained dissolved when the wax mixture was lo h l, t cooled o t crystallization point of the Although the invention has been described with This wax blend had a LSMA c te O respect to the specific embodiments, it is not In the same manner wax blends having an LSM 4O intended that the details thereof shall be .0011- content of 2.5%, 1.0% a d 0.5%, respectively, strued as limitations upon the scope of the invenwere p epa d- For pu p s of oomDoYiSon, tion except to the extent incorporated in the folwax blends containing like concentrations of lowing l im, polyethylene, a commercially employed wax Wh t I claim i modifie i s ad of LSMA, Were p epared. 5 A coating composition comprising a paraffin Evaluation Of the resulting modified waxes emwax and 9, ompletely esterified styrene-maleic p y ne t on l t st m t ds d st uipanhydride heteropolymer made by reacting the merit ve the following results! heteropolymer with a mixture of alcohols ob- Percent Modifier in Wax 0c {at as Tensile Strength, p. s. i., 23 C A Deflection in in. per inch at time of breaking; 0.5 dimension in hori- PE 0136 .0175 .0185 .0229 3123131 position when tested, at }LSMA 0158 .0182 .0307 .0589

Polyethylene The above data show that the LSMA modified tained by hydrogenation of coconut oil, said wax wax, particularly at the 5% concentration, was being present to the extent of from '70 to 99.90 characterized by superior softening point and per cent byvweight cf thetotal weight of the wax and the esterified styrene-maleic anhydride heteropolymer. p 1

References Cited in theme of this patent UNITED STATES'PATENTS Number Name Date 2,454,284 Kirk Nov. 23, 1948 2,599,339 Lippincott et al June 3, 1952 

